Welcome to

Classes
Chemistry

Electrochemistry
Cell Thermodynamics and Electrochemical Series
What you already know
● Reference electrode
● Cell potential (formula)
● Types of electrode potential
What you will learn
● Thermodynamics of a cell
● Gibbs free energy change and cell
potential
● Standard cell potential
● Calculation of electrode potential of
unknown electrodes
● Electrochemical series/ Activity series
● Applications of electrochemical series
 Thermodynamics of a Cell

Cell potential / EMF

EMF is referred to as the vigor with which the cell works

Gibbs free energy change (ΔG) and Cell potential/ EMF

How is ΔG related to spontaneity?

● The free energy change ΔG (a thermochemical quantity) and the cell potential
Ecell (an electrochemical quantity) both measure the driving force of a chemical
reaction.
 Thermodynamics of a Cell
● As studied in thermodynamics, the spontaneity of a reaction at constant
pressure can be predicted by the ΔG or free energy change. For a
spontaneous reaction free energy change is negative (ΔG < 0) or lower the
value of ΔG, higher will be spontaneity.
How is Eocell related to spontaneity?

● Also, for a spontaneous reaction Ecell is positive (Ecell > 0) or higher the value
of Ecell, higher will be spontaneity.
● So, the greater the decrease in free energy greater would be the EMF i.e.,
larger the value of |ΔG| greater will be the value of Ecell.
 Gibbs Free Energy Change and
Cell Potential
Mathematical relation between
Gibbs free energy change (ΔG) and cell potential (EMF)

● The gibbs free energy is defined as the maximum useful work that can be
done.
I.e. |ΔG| = |Maximum useful work|

● Since, for an electrochemical change the work done must be

electrical work done;
so, |ΔG| = |Welectrical|
⇒ |ΔG| = |QTotal × Ecell|
Here, QTotal is the total charge.
 Gibbs Free Energy Change and
Cell Potential

● Since in the electrochemical reactions total charge is due to the electrons

only, hence QTotal = - (number of electrons (Ne) × charge of one electron (e-))
⇒ QTotal = - (Ne × e-)

● As number of electrons (Ne)

= total number of moles (ne) × avogadro number (NA)
⇒ QTotal = - (ne × NA × e-)

● Since, e- (charge on an electron) and avogadro number are constants, they

can be multiplied readily to make the calculation easy. On multiplication,
they give a new constant called Faraday's constant (represented by F). It
represents charge on one mol of electron.
 Gibbs Free Energy Change and
Cell Potential

Charge on 1
electron
= 1.6 × 10-19 C

Charge on 1 mol
electrons (F)
= 1.6 × 10-19 × NA C

= 1.6 × 10-19 × 6.023 × 1023 C

= 96487 C
Gibbs Free Energy Change and
Cell Potential

Charge on 1 mol
electrons (F)
= 96487 C/mol

Charge on 1 mol
electrons (F)
≈ 96500 C/mol

For calculations
 Gibbs Free Energy Change and
Cell Potential
Concept of (ΔG)
ΔG = −nFEcell

At standard state,

ΔG ° = °
−nFEcell

Where Eocell > 0 or positive

and ΔGo < 0 signifies the ΔG°: Standard Gibb's free energy
spontaneity of the reaction.
 Standard Cell Potential

Eocell an intensive property

Mass
Intensive property
independent

So, on multiplying/dividing cell

reaction by any number

Standard electrode potential

value would not change.
 Calculation Of Unknown Electrode Potentials

1st half-cell E °Fe3+ / Fe2+ = x

Let us consider three half cells.
The standard electrode potential
of the two half cells are given and
2nd half-cell E °Fe2+ / Fe = y
we need to find out the standard
electrode potential of the third
cell.
3rd half-cell E °Fe3+ / Fe = ?
 Calculation Of Unknown Electrode Potentials

1st Half-cell

Fe3+(aq) + e− ⇌ Fe2+(aq) ... (1)

n1 = 1

E1° = x
 Calculation Of Unknown Electrode Potentials

2nd Half-cell

Fe2+(aq) + 2e− ⇌ Fe(s) … (2)

n2 = 2

E2° = y
 Calculation Of Unknown Electrode Potentials

3rd Half- cell

Fe3+(aq) + 3e− ⇌ Fe(s) … (3)

n3 = 3

E3° = ?
 Calculation Of Unknown Electrode Potentials

Now, as we Know ΔGo = -nFEocell. So, the standard gibbs free energy change for
the above half cells are as follows.

● For the 1st half cell, ΔG1o = -n1FEo1

⇒ ΔG1o = -(1)F(x) = -xF
Here, ΔG1o = Standard gibbs free energy change for the first half cell
n1 = number of electrons appearing in the reaction of the first half cell.

● For the 2nd half cell, ΔG2o = -n2FEo2

⇒ ΔG2o = -(2)F(y) = -2yF
Here, ΔG2o = Standard gibbs free energy change for the second half cell
n2 = number of electrons appearing in the reaction of the second half cell.
 Calculation Of Unknown Electrode Potentials

● For the 3rd half cell, ΔG3o = -n3FEo3

⇒ ΔG3o = -(2)FEo3

Now, since the reaction (3) can be obtained by adding equation (1) and (2).
Thus,

ΔG°1 + ΔG°2 = ΔG°3

As, ΔG ° is state function

 Calculation Of Unknown Electrode Potentials

Calculation of Eocell

We know,

ΔG ° = °
−nFEcell

Therefore,

−n1FE1 ° + −n2FE2° = −n3FE3°

 Calculation Of Unknown Electrode Potentials

● For the 3rd half cell, ΔG3o = -n3FEo3

⇒ ΔG3o = -(2)FEo3

Now, since the reaction (3) can be obtained by adding equation (1) and (2).
Thus,

ΔG°1 + ΔG°2 = ΔG°3

As, ΔG ° is state function

Calculation Of Unknown Electrode Potentials

n1E°1 + n2E2 °
E3° = n3

1×x+2×y
E°
3 = 3

x + 2y
E°
3 = 3
 Given that = 0.337 V = -0.153 V. Then
Calculate
NEET

Solution

1st half cell

Cu2+ + 2e- ⟶ Cu …(1) ; and Eo1 = 0.337 v

2nd half cell

Cu+ ⟶ Cu2+ + e- …(2) ; and Eo2 = -0.153 v

3rd half cell

Cu+ + e- ⟶ Cu …(3) ; and Eo3 = ? (needs to be find out)
Now, since the reaction (Eq.3 can be obtained on (Eq. 2) + (Eq. 1).
So, ΔG3o = ΔG1o + ΔG2o
⇒ -n3FEo3 = -n1FEo1 + ( -n2FEo2)

⇒
 Given that = -1.51 V and = +1.23 V
Calculate (all in acidic medium)
NEET

Solution

1st half cell

Mn2+ ⟶ MnO4- …(1) ; and E1 = -1.51 v
Now, the above reaction is not balanced and to know the number of
electrons involved we have to balance the reaction. Let us balance the redox
reaction by using ion-electron method

Step 1: Balance the metal atom

The metal atom involved (Mn) is already balanced (1 Mn on each side).
Step 2: Balance the oxygen atoms by adding the sufficient number of H2O
on the other side
Since, there are four oxygen atoms on the product side, so to balance the oxygen
atoms we need to add 4 H2O molecules in the reactant side.
Mn2+ + 4H2O⟶ MnO4-

Step 3: Balance the hydrogen atoms by adding the sufficient number of H+

Now in the above equation, there are 8 hydrogen atoms on the reactant side, so
we need to add 8 H+ in the product side. Mn2+ + 4H2O ⟶ MnO4- + 8H+

Step 4: Balance the charge by adding sufficient number of electron

Total charge on the product side = 8(+1) + (-1) = 7 and +2 on the reactant side
So, we need to add 5 e- on the product side to balance the charge.
Therefore, the overall balanced reaction is as follows.
Mn2+ + 4H2O ⟶ MnO4- + 8H+ + 5e- …(2) ; and E1 = -1.51 v
2nd half cell
MnO2 ⟶ Mn2+ …(3) ; and E2 = 1.23 v

Step 1: Balance the metal atom

The metal atom involved (Mn) is already balanced (1 Mn on each side).

Step 2: Balance the oxygen atoms by adding the sufficient number of H2O
on the other side
Since, there are two oxygen atoms on the reactant side, so to balance the oxygen
atoms we need to add 2 H2O molecules in the product side
MnO2 ⟶ Mn2+ + 2H2O

Step 3: Balance the hydrogen atoms by adding the sufficient number of H+

Now in the above equation, there are 4 hydrogen atoms on the product side, so we
need to add 4 H+ in the reactant side.
MnO2 + 4H+ ⟶ Mn2+ + 2H2O
Step 4: Balance the charge by adding sufficient number of electron
Total charge on the product side = +2
Total charge on the reactant side = 4(+1) = +4
So, we need to add 2 e- on the reactant side to balance the charge.
Therefore, the overall balanced reaction is as follows.
MnO2 + 4H+ + 2e- ⟶ Mn2+ + 2H2O …(4) ; and E2 = 1.23 v

3rd half cell

MnO4- ⟶ MnO2 …(5) ; and E3 = ? (needs to be find out)

Step 1: Balance the metal atom

The metal atom involved (Mn) is already balanced (1 Mn on each side).
Step 2: Balance the oxygen atoms by adding the sufficient number of H2O on the
other side
Since, there are two oxygen atoms on the product side and four oxygen atoms on
the reactant side, so to balance the oxygen atoms we need to add 2 H2O
molecules in the product side
MnO4- ⟶ MnO2 + 2H2O

Step 3: Balance the hydrogen atoms by adding the sufficient number of H+

Now in the above equation, there are 4 hydrogen atoms on the product side, so we
need to add 4 H+ in the reactant side.
MnO4- + 4H+ ⟶ MnO2 + 2H2O
Step 4: Balance the charge by adding sufficient number of electron
Total charge on the product side = 0
Total charge on the reactant side = 4(+1) +(-1) = +3
So, we need to add 3 e- on the reactant side to balance the charge.
Therefore, the overall balanced reaction is as follows.
MnO4- + 4H+ + 3e- ⟶ MnO2 + 2H2O …(6) ; and E3 = ? (needs to be find out)

Now, since the reaction (6) can be obtained on -(Eq .2) - (Eq. 4).
So, ΔG3 = - ΔG1 - ΔG2
⇒ -n3FE3 = - (-n1FE1) - (-n2FE2)

⇒
 Electrochemical Series/ Activity Series

Observations from electrochemical series

● Electrochemical series, also referred to as activity series, is a list that

describes the arrangement of elements in order of their increasing
electrode potential values. Here substances are arranged in the order
of highest reduction potential to the lowest reduction potential.

Fluorine has the highest reduction potential, i.e., a high tendency to

accept electrons and Li has the lowest reduction potential i.e., least
tendency to accept electrons.
 Electrochemical Series/ Activity Series

A negative E° signifies A positive E° signifies

High tendency to get oxidised High tendency to get reduced

That the redox couple is a That the redox couple is a

stronger reducing agent than stronger oxidising agent than
the H+/H2 couple the H+/H2 couple.
 Electrochemical Series/ Activity Series

F Mn Au Hg Ag Cu H Pb Sn Ni Fe Zn Al Mg Na Ca K Li

2.87 1.51 1.40 0.92 0.80 0.52 0.00 -0.13 -0.14 -0.25 -0.44 -0.76 -1.66 -2.36 -2.71 -2.87 -2.93 -3.05

Conclusion from electrochemical series

F 2.87 H 0.00 Li -3.05

Strongest oxidising agent Strongest reducing agent

 Applications of Electrochemical Series

1 The relative oxidising and reducing abilities

of the elements can be compared easily.

Example Zn - Cu system

E 2+ = 0.34 V > E° = −0.76 V

Cu / Cu Zn2+ / Zn

Oxidising power
 Applications of Electrochemical Series

Examples of application 1

1. Cu2+/Cu system has higher tendency to get

reduced i.e., has higher oxidising power

2. Zn2+/Zn system has higher tendency to get

oxidised i.e., has higher reducing power
 Applications of Electrochemical Series

Metal placed lower in the series can displace all elements

2 that lie above it in the series, from their salt solutions.

Examples of application 2

● We cannot store copper sulphate solution in a zinc pot as the solution

oxidises the zinc.

Zn (s) + CuSO4 (aq) ⇌ Cu (s) + ZnSO4 (aq)

 Applications of Electrochemical Series

It helps in the selection of electrode assemblies to

3
construct the galvanic cells of desired EMFs.

Polarity of the electrode system and the electrode

4 reaction can be easily predicted. The anode and
cathode can be identified from the standard electrode
potential and position in the electrochemical series.

Spontaneity and feasibility of the cell can be easily

predicted. As the electrode potential value can be used
5 to calculate the cell potential Eocell . It must be positive
for spontaneous and feasible reactions of a cell.